CN103510135B - A kind of copper foil surface solidification treatment cerium salt composite additive, solid solution and application method thereof - Google Patents
A kind of copper foil surface solidification treatment cerium salt composite additive, solid solution and application method thereof Download PDFInfo
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- CN103510135B CN103510135B CN201310478547.8A CN201310478547A CN103510135B CN 103510135 B CN103510135 B CN 103510135B CN 201310478547 A CN201310478547 A CN 201310478547A CN 103510135 B CN103510135 B CN 103510135B
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Abstract
The invention discloses a kind of copper foil surface solidification treatment cerium salt composite additive, solid solution and application method thereof, it is characterized in that, this additive comprises cerous sulfate, ammonium sulfate and ammoniacal liquor, wherein, in often liter of solid solution, the addition of cerous sulfate is 0.1-1.0g, and the addition of ammonium sulfate is 10-60g, with the ammoniacal liquor metering that concentration is 20%, the addition of ammoniacal liquor is 5-20mL.The present invention utilizes the specific adsorption effect of rare earth ion, makes coating grain refining, and surface is careful, improves oxidation-resistance and the erosion resistance of Copper Foil, for the sustainable development of the industry creates condition.Composite additive of the present invention also has cheapness simultaneously, be easy to the feature carrying out implementing, and the transformation for existing old technique also facilitates feasible, and not needing increases extra technique, does not need to carry out the transformation of any large operational path.
Description
Technical field
The present invention relates to copper foil surface solidification treatment, in particular a kind of copper foil surface solidification treatment cerium salt composite additive and solid solution and application method thereof.
Background technology
At present,---pre-treatment---roughening treatment---solidification (resistance to thermal barrier) process---anti-oxidation process---surface treatment that the surface treatment process of copper foil process that domestic and international each Copper Foil manufacturing enterprise adopts generally can be summarized as: former paper tinsel.
Wherein, solidification treatment is at the single metal of copper foil surface plating thin layer, the process of binary or multicomponent alloy, can according to customer requirement, the kind of the adjustment main salt of plating solution and additive obtains different colours (solidification nickel (black), solidification admiro (canescence) and solidify copper (light red)) cured layer, adopt different processing condition (electroplate liquid compositions, current density, the difference of electroplating time) be cured, the shot copper surface formed at roughening of copper foil forms the ultra tiny single metal or alloy crystallization of one deck, the peel strength of Copper Foil on base material can be strengthened, its main purpose forms one deck blocking layer, Copper Foil is not directly contacted with insulating body, Copper Foil after process and insulating body in conjunction with time, cupric ion can be suppressed to spread to resin layer, improve the oxidation-resistance of Copper Foil and the corrosion resistance nature of coating.
Domestic enterprise is when carrying out surface treatment to electrolytic copper foil, and blocking layer mainly adopts zinc coating.Adopt common zincincation, resistance to heat problem can only be solved, and do not solve the corrosion resisting property problem of Copper Foil completely; When zinc-plated Copper Foil etching, side etching phenomenon can occur, cause the bonding force of Copper Foil and insulating body to decline, time serious, Copper Foil even can come off from insulating body, and this is one of Main Gaps of domestic electrolytic copper foil and external expensive goods performance.In addition, because prussiate galvanizing solution has good dispersive ability and covering power, so far industrially widely use from 20 beginnings of the century always, but plating solution is hypertoxic, serious environment pollution, plating solution reclaims and wastewater treatment is difficult and cost is high, along with people's environmental consciousness is strengthened, plating is just gradually to without cyaniding future development, and the process of surface treatment tool therefore studying electrolytic copper foil is of great significance.
Summary of the invention
For prior art Problems existing, the object of the present invention is to provide a kind of copper foil surface solidification treatment cerium salt composite additive and solid solution and application method thereof.On copper foil surface plating admiro blocking layer, the effect adding additive in the plating solution changes the deposition potential of metal ion and the structure of depositing metal layers.Rare earth element has the electronic structure feature and less electronegativity character that 4f layer do not fill up, the free enthalpy of rare earth and many non-metallic elements is larger negative value simultaneously, chemical affinity is stronger, effectively can improve the performance of conventional plating process plating solution, be easy to produce specific adsorption on the active site of crystal growth, the weave construction of coating is changed.Zn
2+-Ni
2+codeposition shows as Abnormal Codeposition, the specific adsorption of rare earth ion contributes to reducing cathodic deposition current potential, promote the Abnormal Codeposition of zinc-nickel metal ion, this composite additive is used to be cured process to Copper Foil, effectively can improve electrode reaction speed and alloy layer at copper foil surface Structure of the deposits, improve oxidation-resistance and the erosion resistance of Copper Foil.
For achieving the above object, technical solution of the present invention is:
A kind of copper foil surface solidification treatment cerium salt composite additive, this additive comprises cerous sulfate, ammonium sulfate and ammoniacal liquor, wherein, in often liter of solid solution, the addition of cerous sulfate is 0.1-1.0g, the addition of ammonium sulfate is 10-60g, and take concentration as the ammoniacal liquor metering of 20%, the addition of ammoniacal liquor is 5-20ml.
Described additive, the addition of described cerous sulfate is 0.4-0.7g/l, and the addition of described ammonium sulfate is 30-50g/L, and the addition of ammoniacal liquor is 8-15mL.
A solid solution for copper foil surface solidification treatment, this solid solution, using deionized water as solvent, is wherein added with: zinc sulfate 80-160g/L, single nickel salt 20-65g/L, and sodium sulfate 15-60g/L is added with additive described in claim 1 or 2 simultaneously.
Described solid solution, the content of described zinc sulfate is 100-150g/L, and the content of single nickel salt is 30-55g/L, and the content of sodium sulfate is 30-50g/L.
The application method of described solid solution, the working temperature of described solid solution is 15-40 DEG C, and working current density is 2-8A/dm
2.
The application method of described solid solution, the working temperature of described solid solution is 30-35 DEG C, and working current density is 3-6A/dm
2.
Present inventor is through for many years to the research of copper foil surface process curing additive, current environmental requirement (nontoxic, harmless, Sustainable development) is met in guarantee, the composite additive that to have found with rare earth sulfate, ammonium sulfate and ammoniacal liquor be main component, utilize the specific adsorption effect of rare earth ion, make coating grain refining, surface is careful, improves oxidation-resistance and the erosion resistance of Copper Foil, for the sustainable development of the industry creates condition.Composite additive of the present invention also has cheapness simultaneously, be easy to the feature carrying out implementing, and the transformation for existing old technique also facilitates feasible, and not needing increases extra technique, does not need to carry out the transformation of any large operational path.
Accompanying drawing explanation
Fig. 1 is the effect photo of Copper Foil after solidification treatment;
Fig. 2 is Copper Foil 1000 × electron-microscope scanning figure after solidification treatment;
Fig. 3 is Copper Foil 8000 × electron-microscope scanning figure after solidification treatment;
Fig. 4 is electron-microscope scanning figure when adding cerous sulfate 0.2g;
Fig. 5 is for solidification current density is lower than 3A/dm
2time effect photo;
Fig. 6 is for solidification current density is higher than 6A/dm
2time electron-microscope scanning figure.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
The overall craft flow process of copper foil surface process is as follows:
Raw paper tinsel → oil removing → washing → oxide film dissolving → washing → alligatoring → washing → solidification → washing → passivation → washing → hot air drying → silane coating coupling agent, additive of the present invention is used for copper foil surface solidification treatment operation wherein.
Preparation solid solution
Formula one: the deionized water first adding 500ml in 1 liter of plating tank, then the Zinc Sulphate Heptahydrate 130g accurately that weighs is added successively, single nickel salt 35g, sodium sulfate 45g, ammonium sulfate 30-50g, cerous sulfate 0.4-0.7g, ammoniacal liquor (20%) 8-15mL, regulate pH3-4, finally use deionized water constant volume at 1L, make required solid solution.
Formula two: the deionized water first adding 500ml in 1 liter of plating tank, then the Zinc Sulphate Heptahydrate 160g accurately that weighs is added successively, single nickel salt 65g, sodium sulfate 60g, ammonium sulfate 30-50g, cerous sulfate 0.4-0.7g, ammoniacal liquor (20%) 8-15mL, regulate pH3-4, finally use deionized water constant volume at 1L, make required solid solution.
Formula three: the deionized water first adding 500ml in 1 liter of plating tank, then the Zinc Sulphate Heptahydrate 80g accurately that weighs is added successively, single nickel salt 20g, sodium sulfate 15g, ammonium sulfate 30-50g, cerous sulfate 0.4-0.7g, ammoniacal liquor (20%) 8-15mL, regulate pH3-4, finally use deionized water constant volume at 1L, make required solid solution.
The solidification treatment of Copper Foil
Copper Foil in surface treatment process of copper foil after surface coarsening process is put into solidification groove, stereotype does anode, and Copper Foil does negative electrode, by working temperature 30-35 DEG C, current density is 2-8A/dm
2, solidification treatment time 5-50s completes the Passivation Treatment of Copper Foil.
Tested respectively at identical conditions by above three formulas, after respectively carrying out about 30 solidification treatment, the solidification effect of formula one and formula two is constant, and the solidification effect of formula three starts to weaken, and electroplating time is elongated, needs to add main salt; After carrying out about 60 solidification treatment, changing does not appear in the solidification effect of formula one and formula two yet, for avoiding medicine to waste, and screening formulation one.
Fig. 1 is for adopting formula one, solidification working temperature 30-35 DEG C, current density 3-6A/dm
2, solidification treatment time 8-12s is cured the effect photo after process to Copper Foil, Fig. 2, Fig. 3 are electron-microscope scanning figure.
As can be seen from Figure 1, Copper Foil is after solid solution solidification, solidification effect is obvious, surface is in uniform canescence, the formation zn-ni alloy deposits of the shot copper surface uniform formed in roughening treatment then can be found out in electron-microscope scanning figure, Fig. 3 can see trickle zinc-nickel alloy layer crystallization, and regular is arranged in roughened layer surface, strengthens the peel strength of Copper Foil on base material and the erosion resistance of coating.
Present inventor finds through experiment:
When the addition of cerous sulfate exceeds 0.4-0.7g scope, although also form zn-ni alloy deposits, but crystallization is not careful, irregular arrangement, cause copper foil surface conjugation not high, the antioxidant property of coating reduces, after follow-up passivation layer process, place in 200 DEG C of baking ovens and within about 5 minutes, just occur turning yellow, the copper foil surface electron-microscope scanning figure that Fig. 4 is cerous sulfate addition when being 0.2g.
When the current density of solidification is lower than 3A/dm
2time, Copper Foil is elongated for set time, and solidification effect is obvious, but surface evenness is poor, the visible roughened layer color (light red) of middle portion.Fig. 5 is surface effect photo.
When the current density of solidification is higher than 6A/dm
2time, cured layer edge has and significantly burns phenomenon, and cured layer crystal surface microcosmic effect is very irregular, has a strong impact on the antioxidant property of coating.As shown in Figure 6.
Be 100-150g/L according to the content range of zinc sulfate in solid solution of the present invention, the content range of single nickel salt is 30-55g/L, the content range of sodium sulfate is 30-50g/L, as long as select cerous sulfate, ammonium sulfate and ammoniacal liquor addition, solidification working temperature, current density, solidification treatment time in present invention process limited range, treatment effect under the solidification treatment effect of Copper Foil and above-mentioned Fig. 1 optimum process condition is close, all can meet processing requirements.
Should be understood that, for those of ordinary skills, can be improved according to the above description or convert, and all these improve and convert the protection domain that all should belong to claims of the present invention.
Claims (1)
1. a solid solution for copper foil surface solidification treatment, is characterized in that, this solid solution, using deionized water as solvent, is wherein added with: zinc sulfate 80-160g/L, single nickel salt 20-65g/L, sodium sulfate 15-60g/L; This solid solution also comprises additive; Additive sulfur acid sub-cerium, ammonium sulfate and ammoniacal liquor, wherein, in often liter of solid solution, the addition 0.4-0.7g of cerous sulfate, the addition of ammonium sulfate is 30-50g, and take concentration as the ammoniacal liquor metering of 20%, the addition of ammoniacal liquor is 8-15mL;
The working temperature of described solid solution is 15-40 DEG C, and working current density is 2-8A/dm
2.
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| CN109208050B (en) * | 2018-11-02 | 2021-03-30 | 山东金盛源电子材料有限公司 | Surface treatment method for improving corrosion resistance of electrolytic copper foil |
| CN111304709A (en) * | 2020-04-22 | 2020-06-19 | 山东金宝电子股份有限公司 | Surface treating agent for improving corrosion resistance of electrolytic copper foil |
| CN113046794A (en) * | 2021-02-24 | 2021-06-29 | 兰州理工大学 | Method for refining electrodeposited nickel grains by using cerium trichloride |
| CN113046797A (en) * | 2021-03-10 | 2021-06-29 | 四川恒创博联科技有限责任公司 | Electrolytic copper foil additive |
| CN114197000B (en) * | 2021-12-27 | 2023-06-06 | 山东金宝电子有限公司 | Surface treatment method for improving corrosion resistance of electrolytic copper foil |
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| US4101388A (en) * | 1977-03-30 | 1978-07-18 | M & T Chemicals Inc. | Prevention of anode bag clogging in nickel iron plating |
| CN1962944A (en) * | 2006-11-28 | 2007-05-16 | 招远金宝电子有限公司 | Gray surface treatment process for electrolytic copper foil |
| CN101935858A (en) * | 2010-06-23 | 2011-01-05 | 江西理工大学 | Copper foil surface passivation treatment process in copper foil surface treatment process |
| CN102152528A (en) * | 2010-10-21 | 2011-08-17 | 江西理工大学 | Carrier ultrathin copper foil with rare earth modified peel strength and preparation method thereof |
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2013
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Patent Citations (4)
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|---|---|---|---|---|
| US4101388A (en) * | 1977-03-30 | 1978-07-18 | M & T Chemicals Inc. | Prevention of anode bag clogging in nickel iron plating |
| CN1962944A (en) * | 2006-11-28 | 2007-05-16 | 招远金宝电子有限公司 | Gray surface treatment process for electrolytic copper foil |
| CN101935858A (en) * | 2010-06-23 | 2011-01-05 | 江西理工大学 | Copper foil surface passivation treatment process in copper foil surface treatment process |
| CN102152528A (en) * | 2010-10-21 | 2011-08-17 | 江西理工大学 | Carrier ultrathin copper foil with rare earth modified peel strength and preparation method thereof |
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| "稀土在硫酸盐体系电镀锌镍合金中的应用";李付绍等;《表面技术》;20040430;第33卷(第2期);第60-61页第1.2、2.1节 * |
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Effective date of registration: 20200220 Address after: 213341 Jiangsu city of Changzhou province Liyang shezhu Town Industrial Zone Co-patentee after: BUDDHIST TZU CHI GENERAL HOSPITAL Patentee after: JIANGSU MINGFENG ELECTRIC MATERIAL SCIENCE & TECHNOLOGY CO., LTD. Address before: 341000 No. 86 Hongqi Avenue, Jiangxi, Ganzhou Patentee before: BUDDHIST TZU CHI GENERAL HOSPITAL |
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